CN109438643A - A kind of biology base fluorine modified aqueous polyurethane resin and preparation method thereof - Google Patents

A kind of biology base fluorine modified aqueous polyurethane resin and preparation method thereof Download PDF

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Publication number
CN109438643A
CN109438643A CN201811329613.4A CN201811329613A CN109438643A CN 109438643 A CN109438643 A CN 109438643A CN 201811329613 A CN201811329613 A CN 201811329613A CN 109438643 A CN109438643 A CN 109438643A
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polyurethane resin
aqueous polyurethane
modified aqueous
preparation
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CN201811329613.4A
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张武
许钧强
康伦国
姚东生
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Publication of CN109438643A publication Critical patent/CN109438643A/en
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract

The present invention relates to a kind of biology base fluorine modified aqueous polyurethane resin, material composition is polyisocyanates, polyalcohol, oligomer polyol, hydrophilic chain extender, hexafluoroisopropanol, castor oil, polyamine chain extender, neutralizer and deionized water；The present invention also provides a kind of preparation methods of biology base fluorine modified aqueous polyurethane resin；The features such as biology base fluorine modified aqueous polyurethane resin produced by the present invention, the performances that not only have that polyurethane hardness is big, corrosion-resistant, flexibility is good etc., the also low surface with fluorine atom and chemical inertness and castor oil raw material are renewable, at low cost, raising gloss；Fluorine produced by the present invention/castor oil sealing end waterborne polyurethane resin has excellent adhesive force, wearability, water resistance, corrosion resistance, resistance to ag(e)ing, soil resistance, high photosensitiveness and mechanical property, is widely used in woodwork coating, antifouling water-repellent paint, anticorrosive paint and the paint field for requiring high glaze.

Description

A kind of biology base fluorine modified aqueous polyurethane resin and preparation method thereof
Technical field
The present invention relates to a kind of modified aqueous polyurethane more particularly to a kind of biology base fluorine modified aqueous polyurethane resins And preparation method thereof, belong to synthetic resin technical field.
Background technique
Aqueous polyurethane (WPU) is with water for basic medium, and with environmental protection, energy conservation, good mechanical performance, intermiscibility is good, grasps Make the advantages that easy to process, easy to be modified, is widely used to the production fields such as leather finishing agent, spinning coating and adhesive；Its Although haveing excellent performance, there are still costs of material it is high, film water resistance is bad, intensity difference the defects of, it is aqueous poly- in order to improve The performance of urethane, the study on the modification of aqueous polyurethane are increasingly becoming research hotspot in recent years.
Due to petroleum resources worsening shortages and people's environmental consciousness continuous reinforcement renewable resource production biomaterial, Industrial chemicals and fuel increasingly attract the attention of people；The vegetable oil of hydroxyl or hydroxylated vegetable oil are used as polyalcohol Become a kind of novel high polymer shown up prominently in recent years in China in the requirement that the polyurethane of preparation complies fully with environmental protection Material.
Castor oil is a kind of vegetable oil containing hydroxyl, has natural environmental-protective, degradability, reproducibility, resourceful etc. Feature.The castor oil polyhydric alcohol of Beyer Co., Ltd's exploitation can substitute polyether polyol and isocyanates occurs nucleophilic addition and uses In preparing polyurethane material, the dependence to oil product can be not only reduced in this way, improves the added value of castor oil, Er Qiewei The production of polyurethane industrial metaplasia reduces costs, and the development and reduction energy crisis to polyurethane industrial all have highly important Realistic meaning and strategic importance.
Qiang Taotao, Tang Hua etc. disclose the performance and preparation method of a kind of fluorine-containing castor oil-base aqueous polyurethane, with different Buddhist Your ketone diisocyanate, polytetrahydrofuran etc. are primary raw material, using castor oil and Fluorinated dihydric alcohol as modifying agent, using acetone method Fluorine-containing castor oil-base aqueous polyurethane emulsion has been made；But its aqueous polyurethane emulsion prepared, molecular weight are difficult to effectively control, And fluorine atom is located at the centre of resinous molecular structure, is easily wrapped up by other strands, the performance of its unfavorable fluorine characteristic is unfavorable for The hydrophobic and anti-corrosive properties of paint film.
Chinese patent CN103030965A discloses a kind of preparation method of castor oil-base flame resistance polyurethane elastomer, uses Castor oil is raw material, and double bond addition reaction occurs with fire retardant DOPO at 80~160 DEG C, modified castor oil is made；Again with modification Castor oil and di-isocyanate reaction add a certain amount of 200~500 mesh expansible graphite, prepare flame resistance polyurethane elastomer；Tool There is the features such as low in cost and excellent flame retardant effect.
Summary of the invention
The present invention provides a kind of biology base fluorine modified aqueous polyurethane resin.
The present invention also provides a kind of preparation methods of biology base fluorine modified aqueous polyurethane resin.
Since fluorine atom radius is small and has very strong electronegativity, there is shielding protection effect to carbochain, this changes fluorine Property polymer there is excellent thermal stability, weatherability and chemical inertness and unique low surface tension, it is poly- to assign fluorine richness Closing object has excellent hydrophobicity, corrosion resistance and resistance to soiling.
Because of the castor oil containing polar hydroxyl groups, there is good compatibility, low temperature flexibility, heat resistance, water resistance and light The high characteristic in pool, in addition castor oil also has the characteristics that reproducibility, at low cost, can effectively improve the gloss of water-base resin, Solve the problems, such as that water paint gloss is low and at high cost.
The present invention use greenization preparation process, it can be achieved that low emission, low pollution, without byproduct, while use self-emulsifying Method synthesis, is not necessarily to additional emulsifier.
The present invention blocks aqueous polyurethane using castor oil and fluorine atom, and fluorine atom and castor oil introducing is aqueous The both ends of polyurethane, can not only give full play to the characteristic of fluorine atom and castor oil, and can control the molecular weight of polyurethane resin, also Gloss, water resistance and the corrosion resistance of film can be improved；Contain double bond in castor oil simultaneously, can hand in the presence of oxygen Connection accelerates curing reaction, to improve the stemness and hardness of film.
Biology base fluorine modified aqueous polyurethane resin of the present invention includes flexible polyurethane hard segment, polyamine chain extension Section and fluorine end-capping group and castor oil end-capping group；The flexible polyurethane hard segment molecular structure D is as follows:
Wherein, the R1For polyol molecule structure, R2For isocyanate molecule structure, R3For hydrophilic chain extender molecule knot Structure, R4For oligomer polyol molecular structure；The m/n molar ratio is 1:0.2~0.8；The glass of the flexible polyurethane hard segment Glass temperature is 10 DEG C~30 DEG C, and molecular weight is 2500~3000.
The flexible polyurethane hard segment and its molecular structure U after polyamine chain extending reaction are as follows:
Wherein, R is polynary amine structure.
A kind of biology base fluorine modified aqueous polyurethane resin of the invention, molecular structure are as follows:
Wherein, R0For castor oil molecule structure；Biology base fluorine modified aqueous polyurethane resin produced by the present invention, glass Changing temperature is 20 DEG C~65 DEG C, and number-average molecular weight is 8000~15000, pH value 7.5~8.5, and emulsion particle diameter is 30~300nm.
In order to solve the problems, such as that techniques as described above, the present invention take following technical scheme: the present invention relates to a kind of biologies Base fluorine modified aqueous polyurethane resin, by weight, consisting of: 10.0~20.0 parts of polyisocyanates, polyalcohol 3.0~ 8.0 parts, 1.5~4.0 parts of hexafluoroisopropanol, 1.5~4.0 parts of castor oil, 8.0~15.0 parts of oligomer polyol, hydrophilic chain extension 1.5~3.5 parts of agent, 0.01~0.1 part of dibutyl tin dilaurate, 0.5~2.0 part of polyamine chain extender, acetone 3.0~15.0 Part, 1.0~3.0 parts of neutralizer, 45.0~68.0 parts of deionized water.
The polyalcohol is butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, 2- butyl- 2- ethyl -1,3- propylene glycol, 2,4- diethyl -1,5- pentanediol, 2- ethyl -1,3- hexylene glycol, trimethylolpropane, in glycerol One or more of combinations.
The oligomer polyol be molecular weight be 600~3000 polytetrahydrofuran diol, polycarbonate glycol, gather oneself The combination of one or more of interior esterdiol, polyether Glycols.
The hydrophilic chain extender is one of dihydromethyl propionic acid or dimethylolpropionic acid.
The neutralizer is the combination of one or more of triethylamine, ammonium hydroxide, dimethylethanolamine.
The polyamine chain extender is ethylenediamine, two hydrazine of adipic acid, hydrazine hydrate, N, in N- dihydroxy (diisopropyl) aniline One or more of combinations.
The polyisocyanates be toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate, The combination of one or more of benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate.
A kind of preparation method of biology base fluorine modified aqueous polyurethane resin, its step are as follows:
A), in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, it is polynary to sequentially add polyalcohol, oligomer Alcohol is heated to 95~110 DEG C of 1.5~2.0h of vacuum dehydration；
B), 60~70 DEG C of additions polyisocyanates, hydrophilic chain extender are cooled to, dibutyl tin dilaurate is then added dropwise, 80~82 DEG C of 2.0~2.5h of insulation reaction are warming up to, proper amount of acetone is added and adjusts viscosity, is cooled to 70 DEG C, castor oil is added and protects After 0.5~1.0h of temperature reaction, then hexafluoroisopropanol is added dropwise, the reaction was continued 1~2.0h detects nco value, when detection nco value and sets When evaluation is consistent, 40 DEG C or less are cooled the temperature to；
C), neutralizer is slowly added dropwise, after being stirred to react 10~20min, deionized water is added, continues 15~30min of stirring, Then polyamine chain extender is added, is stirred to react 0.5~1.0h, solvent is removed under vacuum, cools down, filters, discharging obtains described Biology base fluorine modified aqueous polyurethane resin.
The present invention develops a kind of biology base fluorine modified aqueous polyurethane resin, not only the big, corrosion resistant with polyurethane hardness Erosion, the performances such as flexibility is good, also have fluorine atom low surface and chemical inertness and castor oil raw material it is renewable, it is at low cost, The features such as improving gloss；Biology base fluorine modified aqueous polyurethane resin produced by the present invention have excellent adhesive force, wearability, Water resistance, corrosion resistance, resistance to ag(e)ing, soil resistance, high photosensitiveness and mechanical property are widely used in woodwork coating, antifouling waterproof applies Material, anticorrosive paint and the paint field for requiring high glaze.
Specific embodiment
A kind of biology base fluorine modified aqueous polyurethane resin of the invention is further described below with reference to embodiment. It is understood that specific embodiment described herein is used only for explaining related invention, rather than the restriction to the invention.
Embodiment 1
A kind of biology base fluorine modified aqueous polyurethane resin, preparation step are as follows:
A), in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, 3.0 parts of butanediol, three hydroxyls are sequentially added 2.0 parts of methylpropane, 10.0 parts of polytetrahydrofuran dihydric alcohol, are heated to 95~110 DEG C of 1.5~2.0h of vacuum dehydration；
B), 60~70 DEG C of 15.0 parts of addition isophorone diisocyanate, 2.6 parts of dihydromethyl propionic acid are cooled to, then It is added dropwise 0.05 part of dibutyl tin dilaurate, is warming up to 80~82 DEG C of 2.0~2.5h of reaction, 10.0 parts of acetone is added and adjusts and glue Degree is cooled to 70 DEG C, after 3.0 parts of insulation reaction 1.0h of castor oil are added, then is added dropwise 2.0 parts of hexafluoroisopropanol, the reaction was continued 1.0h detects nco value, when detection nco value is consistent with design value, cools the temperature to 40 DEG C or less；
C), 2.0 parts of triethylamine, after being stirred to react 20min are slowly added dropwise, 48.85 parts of deionized water is added, continues to stir Then 25min is added 1.5 parts of ethylenediamine, is stirred to react 0.5h, solvent is removed under vacuum, cool down, and filters, discharging, obtains described Biology base fluorine modified aqueous polyurethane resin.
Embodiment 2
A kind of biology base fluorine modified aqueous polyurethane resin, preparation process are as follows:
A), in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, dipropylene glycol 4.0 is sequentially added Part, 1.0 parts of trimethylolpropane, 8.0 parts of polycarbonate glycol, be heated to 95~110 DEG C of vacuum dehydrations 1.5~ 2.0h；
B), 60~70 DEG C of 10.0 parts of addition hexamethylene diisocyanates, 2.0 parts of dimethylolpropionic acid are cooled to, then It is added dropwise 0.05 part of dibutyl tin dilaurate, is warming up to 80~82 DEG C of 2.0~2.5h of reaction, 10.0 parts of acetone is added and adjusts and glue Degree, is cooled to 70 DEG C, after 2.5 parts of insulation reaction 0.5h of castor oil are added, then is added dropwise 2.5 parts of hexafluoroisopropanol, the reaction was continued 2h, Nco value is detected, when detection nco value is consistent with design value, cools the temperature to 40 DEG C or less；
C), 1.5 parts of triethylamine, after being stirred to react 15min are slowly added dropwise, 56.95 parts of deionized water is added, continues to stir Then 20min is added 1.5 parts of two hydrazine of adipic acid, is stirred to react 1h, solvent is removed under vacuum, cool down, and filters, discharging, obtains described Biology base fluorine modified aqueous polyurethane resin.
Embodiment 3
A kind of biology base fluorine modified aqueous polyurethane resin, preparation step are as follows:
A), in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, 3.0 parts of butanediol, glycerol are sequentially added 1.5 parts, 10.0 parts of polycarbonate glycol, are heated to 95~110 DEG C of 1.5~2.0h of vacuum dehydration；
B), 60~70 DEG C of 11.0 parts of addition isophorone diisocyanate, 1.5 parts of dimethylolpropionic acid are cooled to, then It is added dropwise 0.05 part of dibutyl tin dilaurate, is warming up to 80~82 DEG C of 2.0~2.5h of reaction, 10.0 parts of acetone is added and adjusts and glue Degree, is cooled to 70 DEG C, after 3.0 parts of insulation reaction 1h of castor oil are added, then is added dropwise 3.0 parts of hexafluoroisopropanol, the reaction was continued 1.5h, Nco value is detected, when detection nco value is consistent with design value, cools the temperature to 40 DEG C or less；
C), 1.0 parts of triethylamine, after being stirred to react 20min are slowly added dropwise, 53.95 parts of deionized water is added, continues to stir Then 20min is added 2.0 parts of ethylenediamine, is stirred to react 0.8h, solvent is removed under vacuum, cool down, and filters, discharging, obtains described Biology base fluorine modified aqueous polyurethane resin.
According to relevant criterion, in the embodiment of the present invention biology base fluorine modified aqueous polyurethane resin with it is fluorine modified aqueous Polyurethane resin carries out performance comparison, and the performance indicator of detection is as shown in table 1.
Table 1: the embodiment of the present invention and comparative example performance comparison technical indicator
Although the present invention has described it in detail and cited embodiments, but for those of ordinary skill in the art, show Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.

Claims (9)

1. a kind of biology base fluorine modified aqueous polyurethane resin, it is characterised in that: the biology base fluorine modified aqueous polyurethane Resin includes flexible polyurethane hard segment, polyamine chain extension section, fluorine end-capping group and castor oil end-capping group, and molecular structure is such as Shown in lower:
Wherein, the R0For castor oil molecule structure；
The U is the chain extension section after flexible polyurethane hard segment is reacted with polyamine, and molecular structure is as follows:
Wherein, the R is polyamine molecular structure；
The D is flexible polyurethane hard segment, and molecular structure is as follows:
Wherein, the R1For polyol molecule structure, R2For isocyanate molecule structure, R3For hydrophilic chain extender molecular structure, R4 For oligomer polyol molecular structure；The m/n molar ratio is 1:0.2~0.8.
2. a kind of preparation method of biology base fluorine modified aqueous polyurethane resin as described in claim 1, it is characterised in that: described Preparation method, its step are as follows:
A), in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, polyalcohol, oligomer polyol are sequentially added, It is heated to 95~110 DEG C of 1.5~2.0h of vacuum dehydration；
B), 60~70 DEG C of additions polyisocyanates, hydrophilic chain extender are cooled to, dibutyl tin dilaurate is then added dropwise, are heated up To 80~82 DEG C of 2.0~2.5h of insulation reaction, proper amount of acetone is added and adjusts viscosity, is cooled to 70 DEG C, it is anti-that castor-oil plant oil thermal insulating is added After answering 0.5~1.0h, then hexafluoroisopropanol is added dropwise, the reaction was continued 1~2.0h detects nco value, when detection nco value and design value When consistent, 40 DEG C or less are cooled the temperature to；
C), neutralizer is slowly added dropwise, after being stirred to react 10~20min, deionized water is added, continues 15~30min of stirring, then Polyamine chain extender is added, is stirred to react 0.5~1.0h, solvent is removed under vacuum, cools down, filters, discharging obtains the biology Base fluorine modified aqueous polyurethane resin；
By weight, the component of raw material is as follows:
10.0~20.0 parts of polyisocyanates
3.0~8.0 parts of polyalcohol
1.5~4.0 parts of hexafluoroisopropanol
1.5~4.0 parts of castor oil
8.0~15.0 parts of oligomer polyol
1.5~3.5 parts of hydrophilic chain extender
0.01~0.1 part of dibutyl tin dilaurate
0.5~2.0 part of polyamine chain extender
3.0~15.0 parts of acetone
1.0~3.0 parts of neutralizer
45.0~68.0 parts of deionized water.
3. according to claim 1 or 2 any biology base fluorine modified aqueous polyurethane resins, it is characterised in that: the life Object base fluorine modified aqueous polyurethane resin, glass transition temperature are 20 DEG C~65 DEG C, and number-average molecular weight is 8000~15000, pH Value 7.5~8.5, emulsion particle diameter are 30~300nm.
4. preparation method according to claim 2, it is characterised in that: the polyalcohol is butanediol, hexylene glycol, new penta 2 Alcohol, Diethylene Glycol, dipropylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,4- diethyl -1,5- pentanediol, The combination of one or more of 2- ethyl -1,3- hexylene glycol, trimethylolpropane, glycerol.
5. preparation method according to claim 2, it is characterised in that: the oligomer polyol be molecular weight be 600~ At least one of 3000 polytetrahydrofuran diol, polycarbonate glycol, polycaprolactone glycol, polyether Glycols.
6. preparation method according to claim 2, it is characterised in that: the hydrophilic chain extender is dihydromethyl propionic acid, two One of hydroxymethylbutyrate.
7. preparation method according to claim 2, it is characterised in that: the neutralizer is triethylamine, ammonium hydroxide, dimethyl second At least one of hydramine.
8. preparation method according to claim 2, it is characterised in that: the polyamine chain extender is ethylenediamine, adipic acid Two hydrazines, hydrazine hydrate, N, at least one of N- dihydroxy (diisopropyl) aniline.
9. preparation method according to claim 2, it is characterised in that: the polyisocyanates be toluene di-isocyanate(TDI), Isophorone diisocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate two are different At least one of cyanate.
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CN112646114A (en) * 2020-12-18 2021-04-13 合众（佛山）化工有限公司 Triplecene derivative modified polyurethane aqueous resin and preparation method thereof
CN112679702A (en) * 2021-01-06 2021-04-20 上海应用技术大学 Fluorine-containing epoxy resin curing agent and preparation method thereof
CN116285637A (en) * 2023-04-10 2023-06-23 齐鲁工业大学(山东省科学院) High-strength anticorrosion aqueous polyurethane, anticorrosion material and application
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